Method for controlling growth of undesired vegetation



United States Patent r 3,169,849 BETH-18D FOR CGNTIROLLENG GRGWTH OF UNDESIRED VEGETATEQN Alan I. Lemin, Richland Township, Kalamazoo County, Mich assignor to The Upjohn Company, Kalamazoo, Mich, a corporation of Michigan No Drawing. Filed July 9, 1958, Ser. No. 747,362 12 Claims. (Cl. 71--2.6}

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wherein R and R represent lower aliphatic hydrocarbon radicals, such that the total number of carbon atoms in the radicals R and R is not less than five and not more than twelve, are effective for the control of undesired vege- I tation. The term lower aliphatic hydrocarbon radical is intended to mean an acyclic or cyclic aliphatic hydrocarbon radical containing up to eleven carbon atoms, which radical can be saturated or unsaturated. Such radicals include alkyl radicals, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and isomeric forms thereo; alkenyl radicals, for example, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, monenyl, decenyl, undecenyl, and isomeric forms thereof; alkynyl radicals, for example, ethnyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, and isomeric forms thereof; and cycloaliphatic radicals, for example, cyclobutyl, cyclopentyl, cyclopentenyl, methylcyclopentyl, cyclohexyl, dimethylcyclohexyl, cycloheptyl, and isomeric forms thereof.

It is an object of the invention to provide novel herbicidal compositions which contain as active ingredient at least one of the compounds of the Formul I. It is a further object of the invention to provide a method of controlling undesired vegetation by applying to such vegetation at least one of the compoundshaving the Formula 1. Other objects of the invention will be apparent to those skilled in the art to which this invention pertains.

The preparation of many of the compounds included within the Formula I has been described in the literature although it has not previously been recognized that these compounds possess herbicidal activity. The previously known compounds having the Formula I include n-butyl 2-methoxy-benzoate, n-amyl 2-methoxyoenzoate, ethyl B-n-butoxybenzoate, ethyl 3-n-amyloxybenzoate, methyl 4-n-butoxybenzoate, methyl 4-isobutoxybenzoate, methyl 4-sec-butoxybenzoate, methyl 4-n-amyloxybenzoate, methyl 4-isoamyloxybenzoate, methyl 4-n-hexyloxy benzoate, methyl 4-n-octyloxybenzoate, ethyl 4-n-prop0xybenzoate, ethyl 4-isopropoxybenzoate, ethyl 4-n-butoxybenzoate, ethyl 4-isobutoxybenzoate, ethyl 4-sec-butoxybenzoate, ethyl 4-n-amyloxybenzoate, ethyl 4-isoamyloxybenzoate, ethyl 4-n-hexyloxybenzoate, ethyl 4-n-heptyloxybenzoate, ethyl 4-n-octyloxybenzoate, ethyl 4-(l-methylheptyloxy)benzoate, ethyl 4-isooctyloxybenzoate, ethyl 4-n-nonyloxybenzoate, ethyl 4-n-decyloxybenzoate, npropyl 4-ethoxybenzoate, n-butyl 4-methoxybenzoate, isobutyl 4-methoxybenzoate, tert-butyl 4-methoxybenzoate, n-amyl 4-rnethoxybenzoate, isoamyl 4-methoxybenzoate, n-heptyl 4-methoxybenzoate, ethyl 2-allyloxybenzoate, allyl Z-allyloxybenzoate, n-butyl 3-(2-methallyloxy)benzoate, ethyl 4-allyl0xybenzoate, ethyl 4-(l-methallyloxy) benzoate, ethyl 4-(2-butenyloxy)benzoate, ethyl 4-(1- ethylallyloxy)benzoate, ethyl 4-(2-pentenyloxy)benzoate, ethyl 4-(l-methyl-Z-butenyloxy)benzoate, ethyl 4-(3- methyl-Z-butenyloxy)benzoate,. ethyl 4-(l-propylallyloxy)benzoate, ethyl 4-(2-hexenyloxy)benzoate, butyl 4- (Z-methallyloxy)benzoate, 3-butynyl 4-methoxybenzoate, cyclohexyl 2-methoxybenzoate, cyclohexyl 2-ethoxybenzoate, cyclohexyl 3-methoxybenzoate, cyclohexyl 3 ethoxybenzoate, cyclohexyl 4-methoxybenzoate, cyclohexyl 4-ethoxybenzoate, methyl 4-cyclohexyloxybenzoate, ethyl 4-cyclohexyloxybenzoate, ethyl 4-cyclopentyloxybenzoate, and l-methylheptyl Z-methoxybenzoate.

Many of the compounds which are included Within the Formula I are novel. The novel compounds include ethyl 2-n-propoxybenzoate, ethyl 2-n-propoxybenzoate, ethyl Z-n-heptyloxybenzoate, n-propyl 2-n-propoxybenzoate, npropyl Z-n-butoxybenzoate, n-propyl 2-n-amyloxybenzo ate, n-propyl Z-n-hexyloxybenzoate, n-propyl Z-n-heptyloxybenzoate, n-butyl Z-ethoxybenzoate, n-butyl 2-n-propoxybenzoate, n-butyl Z-n-butoxybenzoate, n-amyl 2- ethoxybenzoate, n-amyl Z-n-propoxybenzoate, n-amyl 2 n-amyloxybenzoate, n-amyl Z-n-hexyloxybenzoate, n-amyl Z-n-heptyloxybenzoate, isoamyl Z-n-propoxybenzoate, nhexyl 2-ethoxybenzoate, n-hexyl Z-n-propoxybenzoate, nhexyl Z-n-butoxybenzoate, n-butyl 4n-propoxybenzoate, n-butyl 4-n-amyloxybenzoate, n-propyl Q-allyloxybenzoate, n-butyl 2-allyloxybenzoate, n-amyl 2-allyloxybenzo ate, isoamyl 2-allyloxybenzoate, n-hexyl 2-allyloxybenzoate, n-octyl 2-allyloxybenzoate, n-butyl 2-(2-methallyl oxy)benzoate, n-butyl 4-allyloxybenzoate, n-amyl 4-allyloxybenzoate, n-hexyl 4-allyloxybenzoate, n-butyl 3-allyloxybenzoate, and n-butyl 3-n-propoxybenzoate.

The novel compoundsof Formula I can be prepared by methods which are well-known in the art. Thus the'compounds of Formula I can be prepared by etherification of the corresponding hydroxybenzoic esters having the formula:

COOR

where R has the significance hereinbefore defined, using conventional methods for the etherification of phenols. For example, the hydroxybenzoic acid esters of the above formula can be reacted with a halide of the formula R X, wherein R has the significance hereinbefore defined and X represents a halogen atom, in the presence of a base such as an alkali metal hydroxide, an alkali metal carbon- COOH wherein R has the significance hereinbefore described, using conventional procedures for the preparation of esters of aromatic carboxylic acids. For example, the hydroxybenzoic acid ethers of the above formula can be converted to the acid chlorides using reagents such as thionyl chloride, phosphorus trichloride phosphorus pentachloride, and the like, and the acid chlorides can he reacted with an alcohol of the formula ROI-I where R has the significance hereinbetore defined. Both the hydroxybenzoic acid esters and the O-ethers of hydroxybenzoic acids of the above general formulae, many of which are described in the literature, can themselves be obtained from the corresponding hydroxybenzoic acids by conventional methods. Thus the hydroxybenzoic acids can be etherified or esterified by the procedures described above. Hence, using the stages ofetherification and esterification outlined above, in either sequence, it is possible to pass Formula I in two stages. Other methods for the prepara tion of the compounds of Formula I will be obvious to the skilled chemist.

The compounds having the Formula I above show herbicidal activity and can be used to control undesirable vegetation. By undesirable vegetation is meant not only plants which are commonly regarded as weeds wherever they may grow, but also certain plants which are not normally regarded as weeds except when they are found growing on land which is supporting more valuable plants, for example, horticultural and agricultural crops. The compounds having the Formula I show particularly valuable activity against undesirable vegetation such as crabgrass, white clover, oxalis, chickweed, foxtail, Poa anmar, and the like, but do not cause any significant damage to desirable lawn grasses such as rye, fescue, Kentucky blue grass, and the like, and to crops such as corn, beans, and the like, when applied in concentrations which destroy the crabgrass and other undesirable vegetation. The compounds having the Formula I find particular application for the selective control of crabgrass growing in lawns. The compounds having the'Formula I in which the total number of carbon atoms in the radicals R and R is within the range seven to nine show particularly valuable properties in this respect. Such compounds include n-butyl 2- allyloxybenzoate, n-butyl 2-n-propoxybenzoate, n-amyl 2-allyloxybenzoate, and'ethyl 2-n-heptyloxybenzoate.

The herbicidal activity of the compounds having the Formula I is illustrated by the results of the following test. The test was carried out by spraying mixed plantings of seedling crabgrass and the desirable lawn grasses, rye,

fescue, and bluegrass, to run oil with an aqueous dispersion of the compound under test at a concentration of 2000 parts per million (0.2 percent). The spray solution contained approximately 300 to 600 parts per million (0.03 to 0.06 percent) of Triton X-lOO (a proprietary surfactant which is an alkylaryl polyether alcohol). The plants were examined two to four weeks after the application of the test compound and their condition was recorded on an arbitrary scale of (no effect) through (all plants dead).

aieasae from a hydroxybenzoic acid to the desired compound of I i The results are recorded in Table I.

TABLE 1 Crabgrass Rye Fescue Bluegrass n-Propyl 2-allyloxybenzoate 2 n-Butyl Z-allyloxybenzoate-.- n-Arnyl 2a11yloxyb enzoaten Isoamyl 2-allyloxybenzoate.-- n-Hexyl 2-allyloxybenzoate.-- n-Octyl 2-allyloxybenzoate n-Butyl 3-ally10xybenzoate n-Butyl 2-(2-rnethallyloxy) benzoate n-Butyl i-allyloxybenzoate n-Amyl 4-allyloxybenzoate n-Hexyl 4allyloxybenzoate n-Butyl 4-n-propoxybenzoate n-Butyl i-n-arnyloxybenzoate Ethyl Z-n-propoxybenzoete... Ethyl Z-n-heptyloxybenzoate I n-Propyl Z-n-propoxybenzoate n-Propyl Z-n-butoxybenzoate; n-Propyl 2-n-amyloxybenzoat-e n-Propyl Z-n-hexyloxybenzoate n-Propyl Q-n-heptyloxybenzoate 2 n-Butyl Z-ethoxyhenzoata. 1-2 n-Butyl 2-n-propoxybenzoate n-Butyl Z-n-butoxybenzoate. n-Amyl 2-ethoxybenzoate l n-Amyl 2-11-ptopoxybenzoate n-Amyl Q-n-amyloxybenzoate n-Arnyl 2-n-hexyloxybenzoate n-Amyl Z-n-heptyloxybenzoate Isoamyl 2-n-propoxybenzoate n-Hexyl 2-ethoxybenzoate n-Hexyl Z-n-propoxybenzoate n-Hexyl Q-n-butoxybenzoaten-Butyl 3-n-propoxybenzoate [0 CL, PP- Nw C menace:

o PLOHOOOHOHHN O v i-orat oncoca For the selective control of undesired vegetation the compounds having the Formula I above as applied at a rate within the range of about 0.02 to about pounds per acre, the preferred rate of application being about 0.2 to about ten pounds per acre.

For the non-selective control of undesired vegetation the compounds having the Formula I above are applied at a rate within the range of about one to about pounds per acre, the preferred rate of application being about 2.5 to about thirty pounds per acre.

In order to achieve the maximum herbicidal effect of the compounds having the Formula I above it is necessary to formulate the compounds in compositions which can be freely applied to vegetation and evenly distributed over the surface thereof. Acordingly the method of preparation of the herbicidal compositions of the invention is a matter of importance.

The herbicidal compositions of the invention comprise as active ingredient at least one compound having the formula:

COOR

radicals, such that the total number of carbon atoms in the radicals R and R is not less than five and not more 1 than twelve, in association with a carrier material.

Where the compositions are to be employed as selective herbicides it is-advantageous that the carrier material be phytonomic, that is to say, a carrier which can be applied to plants without phytotoxicity or other adverse effects. Where the compositions are to be employed as general herbicides such considerations do not apply.

The herbicidal compositions of the invention can take the form of dusts which are prepared by intimate admixture of the active ingredient with a solid carrier or extender which maintains the compositions in a dry, freeflowing state. Since the compounds having the Formula I are ordinarily liquids, the herbicidal dusts of the inven- .tion can be prepared more conveniently by adding to the solid diluent a solution of the compound in a volatile solvent such as ethanol, acetone, ether, and the like, mixing to form a paste, drying and milling. The solid carriers which can be used include the natural clays such as china clay and bentonite, minerals in the natural state such as talc, pyrophyllite, quartz, diatomaceous earth, fullers earth, chalk, and rock phosphate, and the chemically modified minerals such as washed bentonite, precipitated calcium phosphate, precipitated calcium carbonate, and colloidal silica. The solid diluents which can be employed in the compositions also include solid artificial fertil zers. Such solid compositions can be applied to vegetation in the form of dusts by use of conventional machinery. A preferred solid composition is one which also comprises a surfactant. Such compositions can be added to water to form aqueous dispersions which can be applied to vegetation by conventional spraying machines. The surfactants which can be employed in the preparation of such compositions include alkyl sulfates and sulfonates, alkylbenzenesulfonates, sulfosuccinate esters, polyoxyethylene sulfates, polyoxyethylene sorbitan monolaurate, alkylarylpolyether sulfates, alkylarylpolyether alcohols, alkylnaphthalenesulfonates, alkyl quaternary ammonium salts, sulfated fatty acids and esters, sulfated fatty acid amides, glycerol mannitan laurate, polyalkylether condensates of fatty acids, and lignin sulfonates', the sulfates and sulfonates, of course, being used in the form of the soluble salts, for example, their sodium salts.

The herbicidal compositions of the invention also comprise aqueous emulsions. The aqueous emulsions can be prepared by dissolving a surfactant of the type noted above in a compound having the Formula I and pouring the emulsifiable concentrate so obtained into water with vigorous agitation. The aqueous emulsions of the invention can also be prepared by dissolving the active ingredient in a water-miscible solvent such as Carbitol (diethyL ene glycol monoethyl ether), acetone, a lower alkanol, Cellosolve (ethylene glycol monoethyl ether), dioxan, and the like, if desired, in association with a surfactant such as noted above, to obtain an emulsifiable concentrate which is poured into water with vigorous agitation. The aqueous emulsions of the invention can also be prepared by dissolving the active ingredient and a surfactant such as noted above in an organic solvent which is immiscible with water. The resulting emulsifiable concentrate is then admixed with water with vigorous agitation to form an emulsion. The water-immiscible organic solvents which are suitable for use include cyclohexanone, summer oils, aromatic hydrocarbons such as benzene, toluene, xylene, and high-boiling petroleum hydrocarbons such as kerosene, diesel oil, and the like.

The aqueous emulsions of the invention can be supplied to the user in the form of the emulsifiable concentrates described above which require dilution with water before use. Both the concentrated compositions and the diluted compositions are included within the scope of the present invention.

The compositions of the invention which are intended for use in the form of aqueous dispersions or emulsions can also comprise a humectant, that is to say, an agent which will delay the drying of the composition in contact with the vegetation to which it has been applied. Suitable humectants include glycerol, diethylene glycol, solubilized lignins such as calcium lignosulfonate, and the like.

The exact concentration of active ingredient in any of the compositions of the invention is not critical and may vary considerably, provided the active ingredient is applied to the vegetation to be treated at a rate within the range defined above. However, in general it has been found advantageous to employ concentrations of active ingredient of the order of 1,000 to 10,000 parts per million (0.1-1.0 percent) in the aqueous emulsions or dispersions used for the treatment of vegetation. The concentration of active ingredient in the concentrates from which these compositions are prepared can be as high as 99.5 percent by weight. The concentration of active ingredient in the dust formulations of the invention is limited by the generally oily nature of the compounds having the Formula I. However, the concentration of active ingredient in the dust formulations of the invention is advantageously of the order of about one to fifteen percent by weight.

The concentrations and the rates at which the compositions of the invention are applied will of course vary in accordance with factors such as the nature of the 'vegetation being treated, whether the treatment is a selective one, the season of the year at which the treatment is made, and the nature of the machine which is used to apply the compositions.

The compositions of the invention can also include compositions in which the active ingredients of the above Formula I are employed in combination with known herbicides. Such known herbicides include 2,4-dichloro phenoxyacetic acid, 2 methyl 4 chlorophenyoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid, ammonium sulfamate, ammonium thiocyanate, dinitro-o-cresol, sodium arsenite, phenylmercuric acetate, isopropyl N-phenylcarbamate, isopropyl N-(3-chlorophenyl)carbamate, 3 (p-chlorophenyl)-1,1-dimethylurea, trichloroacetic acid, 2,2-dichloropropionic acid, sodium pentachlorophenate, sodium chlorate, and chlordane.

The following examples are illustrative of the proc ess and compositions of the present invention, but are not to be construed as limiting.

A. PREPARATION OF NOVEL COMPOUNDS OF THE FORMULA I Preparation 1.-n'-Butyl 4-allyloxybenzoale A mixture of 48.5 grams (0.25 mole) of n-butyl 4- hydroxybenzoate, 33.3 grams (0.275 mole) of allyl bromide, 38 grams (0.275 mole) of anhydrous potassium carbonate and 350 milliliters of acetone was heated under reflux for sixteen hours. The resulting mixture was allowed to cool before being treated With 200 milliliters of ether and 200 milliliters of Water. The mixture was shaken and the ether layer was separated, washed twice with fifty milliliters of ten percent aqueous potassium hydroxide solution, once With fifty milliliters of two percent hydrochloric acid, and then with -millilitcr portions of water until the washings were neutral. The ethereal solution was finally dried over anhydrous sodium sulfate and evaporated to dryness. The residual oil was distilled under reduced pressure. There was thus obtained 36 grams of n-butyl 4-allyloxybenzoa'te in the form of a liquid having a boiling point of to 113 degrees centigrade at a pressure of 0.05 millimeter of mercury; n =l.5l82.

Analysis.Calcd. for C I-1 0 C, 71.77; H, 7.74. Found: C, 71.68; H. 7.56.

Preparation 2.n-Am-yl 4-allyl0xy'benz0ate (a) PREPARATION OF N-AMYL 4-HYDROXYBENZOATE A mixture of 69 grams (0.5 mole) of 4-hydroxybeuzoic acid, 440 grams (5 mole) of n-aniyl alcohol and twenty milliliters of concentrated sulfuric acid was heated under reflux for five hours. The resulting mixture was allowed to cool, treated with one liter of water and shaken. The upper layer was separated, washed twice with one-liter sues-teas portions'of saturated aqueous sodium bicarbonate solution andoncewith one liter of Wateni The organic layer wasjdried 'over anhydrous sodium sulfate and then distilled under reduced pressure. There was thus obtaincd n-amyl 4 hydroxybenzoate in the form of an oil which had a boilingpoint of 165 to .167 degrees centigrade at a pressure of one to 1.5 millimeters of mercury. Analysis;-Calcd. for C I- C, 69.21; H, 7.74. Found: C, 68.78; H, 7.95.

1(1) PREPARATION OF N-AMYL 4 ALLYLOXYBENZOATE -Using the procedure described in Preparation 1, but employing 20.8 grams (0.1 mole) of n-arnyl 4-hydroxy- ,benzoate. (prepared as described above), 13.4 grams (0.11 mole) of allyl bromide, 13.9 grams (0.1 mole) of anhydrous potassium carbonate and 150 milliliters of acetone, there was obtained n-amyl 4-allyloxybenzoate in the form of an oil having a boiling point of 133 to 136 degrees centrigrade at a pressure of 0.06 millimeter of mercury; n =1.5141.

Analysis.-Calcd. for C H O C, 72.55; H, 8.12. Found: C, 72.32; H, 8.34.

Preparation 3..'z-Hexyl 4-allyloxyberzzoate n-Hexyl 4-hydroxybenzoate was obtained by the process described in Preparation 2(a), but substituting n-hexyl alcohol for n-amyl alcohol, in the form of an oil having a boiling point of 154 to 156 degrees centigrade at a pressure of 0.25 millimeter of mercury. Using the procedure described in Preparation 1, but substituting the n-hexyl 4-hydroxybenzoate prepared as described above for n-amyl 4-hydroxybenzoate, there was obtained n-hexyl 4-allyloxybenzoate in the form of an oil having a boiling point of 127.5 to 128.5 degrees centrigrade at a pressure of 0.2 millimeter of mercury.

Analysis.Calcd. for C H O z C, 73.25; H, 8.45. Found: C, 73.53; H, 8.64.

Preparation 4.n-Propyl Z-allyloxybenzoate Using the procedure described in Preparation 1, but substituting n-propyl salicylate for n-butyl 4-hydroxybenzoate, there was obtained n-propyl 2-allyloxybenzoate in the form of an oil having a boiling point of 96 to 102 degrees centigrade at a pressure of 0.1 millimeter of mercury; n *=1.5 176.

Analysis.-Calcd. for C H O C, 70.89; H, 7.32. Found: C, 68.95; H, 7.22.

Preparation .n-Butyl Z-allyloxybmzoate Using the procedure described in Preparation 1, but substituting n-butyl salicylate for n-butyl 4-hydroxybenzoate, there was obtained n-butyl 2-allyloxybenzoate in the form of an oil which had a boiling point of 113 degrees Centigrade at a pressure of 0.1 millimeter of mercury; n *=1.5145.

Analysis.Calcd. for C I-1 0 C, 71.77; H, 7.74. Found: C, 71.25; H, 7.73.

Preparation 6 .n-Amyl Z-allyloxybenzoote Preparation 7.-Is0amyl Z-allyloxybenzoaie Using the procedure described in Preparation 1, but

o w substituting isoamyl salicylate for n butyl 4-l1ydroxybenzoate, there was obtained isoamyl 2 allyloXyben'zoate in the forrnof an oil having a boiling point of 101 to 103 degrees centigrade at a pressure ot 0.1 millimeter of mercury; .11 =1.'5078.

'AnaIysz's;'Calcdf for C H O C, 72.55; H, 8.12. FoundzfC, 71.93;1-1, 7.87. i

Preparation 8.n-Hexyl Z-allyloxybenz oate n-Hexyl salicylate was obtained, using the procedure described in Preparation 2(a) but substituting salicylic acid for 4-hydr0Xybenzoic' acid and n-hexyl alcohol for n-amyl alcohol, in the form of an oil having a boiling point of 109 to 113 degrees centigrade at a pressure of 0.4 millimeter of mercury. Using the procedure described in Preparation 1, but substituting n-hexyl salicylate for ri-butyl 4-hy'droxybenzoate, there was obtained n-hexyl 2-allyloxybenzoate in the form of an oil having a boiling point of 124 to 127 degrees centigrade at a pressure of 0.2 millimeter of mercury.

- Analysis.Calcd. for C H O C, 73.25; H, 8.45. Found: C, 72.11; H, 8.36;

Preparation 9.n-Octyl' Z-allyloxybcnzotzte n-Octyl salicylate was obtained, using the procedure described in Preparation 2(a) but substituting salicylic acid for 4-hydroxybenzoic acid and n-octyl alcohol for n-amyl alcohol, in the form of an oil having a boiling point or" 121 to- 124 degrees centigrade at a pressure of 0.19 millimeter of mercury. Using the procedure described in l reparation 1, but substituting n-octyl salicylate tor n-butyl 4-hydroxybenzo'ate and methyl ethyl ketone for acetone, there was obtained n-octyl '2-allyloxybenzoate in the form of an oil having a boiling point of 137 to 139 degrees centigrade at a pressure of 0.1 millimeter of mercury; n =l.5000.

Analysis.--Calcd. for (3 1-1 0 C, 74.44; H, 9.03. Foundz C, 74.16; H, 8.98.

Preparation J0.rr-Bz:tyl 4-n-pr0p0xybenz0ate Using the procedure described in Preparation 1, but substituting l-bromopropane for allyl bromide, there was obtained n butyl 4-n-propoxybenzoate in the form of an oil having a boiling point of 110 to 111 degrees centigrade at a pressure of 0.2 millimeter of mercury; n =1.5058.

Analysis.-Calcd. for C H O C, 71.16; H, 8.53. Found: C, 71.21; H, 8.48.

Preparation. 11.n-Butyl 4-11-amyl0xybenzoate V Preparation 12.-Ethyl Z-n-propoxybehzoate A mixture of 33.2 grams (0.2 mole) of ethyl salicylate, 27.06 grams (0.22 mole) of l-bromoproparie, 27.6 grams (0.2 mole) of anhydrous potassium carbonate, 33 grams (0.22 mole) of sodium iodide and 280 milliliters of acetone Was heated under reflux for sixteen hours. The mixture was allowed to cool, one liter of Water was added and'the'product was shaken with 500 milliliters of ether. Theethereal solution was washed successively with two portions, each of milliliters, of ten percent aqueous sodium hydroxide solution, fifty milliliters of two percent hydrochloric acid, and with portions of 200 milliliters of water until the washings were neutral; The ethereal solution Wasdried over anhydrous sodium sulfate and the solution ias evaporated to dryness. The oily residue was distilled under reduced pressure to yield 2.35 grams of ethyl Z-n-propoxybenzoate in theform of an oil having a boiling point of 97 to 101 degrees centigrade at a pressure of 0.8 millimeter of mercury; n =1.5O49.

Analysis.-Calcd. for C H O C, 69.21; H, 7.74. Found: C, 68.77; H, 7.70.

Preparation 13.-Ethyl Z-n-heptyloxybenzoate Using the procedure described in Preparation 12, but substituting n-heptyl bromide for l-brornopropane, there was obtained ethyl Z-n-heptyloxybenzoate in the -form of an oil having a boiling point of 110 to 114 degrees centigrude at a pressure of 0.15 millimeter of mercury; n =1.4955.

Analysis.-Calcd. for C16H2g031 C, 72.69; H, 9.15. Found: C, 72.59; H, 9.13.

Preparation 14.n-Prpyl Z-n-propoxybenzoate Using the procedure described in Preparation 1, but substituting n-propyl salicylate for n-butyl 4-hydroxybenzoate and 1-bromopropane for allyl bromide, there was obtained n-propyl 2-n-propoxybenzoate in the form of an oil having a boiling point of 97 degrees centigrade at a pressure of 0.15 millimeter of mercury; n: =l.5052.

Analysis.-Calcd. for C I-1 0 C, 70.24; H, 8.16. Found: C, 69.82; H, 8.14.

Preparation 15.n-Pr0pyl Z-n-butoxybenzoate Preparation 16.n-Pr0pyl Z-n-amyloxybenzoate Using the procedure described in Preparation 1, but substituting n-propyl salicylate for n-butyl 4-hydroxybenzoate and n-amyl bromide for allyl bromide, there was obtained n-propyl Z-n-amyloxybenzoate in the form of an oil having a boiling point of 115 to 117 degrees centigrade at a pressure of 0.1 millimeter of mercury; 121327: 1.4980.

Analysis.-Calcd. for C H O C, 71.97; H, 8.86. Found: C, 72.15; H, 8.76.

Preparation ]7.n-Propyl Z-n-hexyloxybenzoate Using the procedure described in Preparation 1, but substituting u-propyl salicylate for n-butyl 4-hydroxybenzoate and n-heXyl bromide for allyl bromide, there was obtained n-propyl Z-n-hexyloxybenzoate in the form of an oil having a boiling point of 118 degrees centigrade at a pressure of 0.06 millimeter of mercury; n =1.4979.

Analysis.Calcd. for C H O C, 72.69; H, 9.15.

Found: C, 73.07; H, 9.56.

Preparation I8.-n-Pr0pyl Z-n-heptyloxybenzoate Using the procedure described in Preparation'l, but

substituting n-propyl salicylate for n-butyl 4-hydr0xybenzoate, n-heptyl bromide for allyl bromide and methyl ethyl ketone for acetone, there was obtained n-propyl Z-n-heptyloxyberzoate in the form of an oil having a boiling point of 130 to 131 degrees centigrade at a pressure of 0.2 millimeter of mercury; n =1.4927.

Analysis.-Calcd. for C H O C, 73.34; H, 9.41.

Found: C, 73.27; H, 9.34.

Preparation 19.n-Bntyl Z-ethoxybenzoate Using the procedure described in Preparation 1, but

substituting n-butyl salicylate for n-butyl 4-hydroXyben-- zoate, ethyl iodide for allyl bromide and methyl ethyl ketone for acetone, there was obtained n-butyl 2-ethoxybenzoate in the form of an oil having a boiling point of 10 96 to 103 degrees centigrade at a pressure of 0.1 millimeter of mercury; n =1.50'40.

Analysis.Calcd. for C I-1 0 C, 70.24; H, 8.16. Found: C, 70.66; H, 7.73.

Preparation 20.--n-Butyl Z-n-propoxybenzoate Using the procedure described in Preparation 1, but substituting n-butyl salicylate for n-butyl 4-hydroxybenzoate and l-bromopropane for allyl bromide, there was obtained n-butyl 2-n-propoxybenzoate in the form of an oil having a boiling point of 116 to 119 degrees centigrade at a pressure 'of 0.5 millimeter of mercury; n =1.5028.

Analysis.-Calcd. for C H O C, 71.16; H, 8.53. Found: C, 70.89; H, 8.18.

Preparation 21.n-Butyl Z-n-butoxybenzoate Using the procedure described in Preparation 12, but substituting n-butyl salicylate for ethyl salicylate, n-butyl bromide for l-bromopropane and methyl ethyl ketone for acetone, there was obtained n-butyl 2-n-butoxybenzoate in the form of an oil having a boiling point of 105 to 107 degrees centigrade at a pressure of 0.12 millimeter of mercury; n =1.5043.

Analysis.-Calcd. fOI' C15H22O3: C, H, 8.86- Found: C, 71.29; H, 7.78.

Preparation 22.-n-Amyl Z-ethovcybenzoate Using the procedure described in Preparation 1, but substituting n-amyl salicylate for n-butyl 4-hydroxybenzoate, ethyl iodide for allyl bromide and methyl ethyl ketone for acetone, there was obtained n-amyl 2-ethoxybenzoate in the form of an oil having a boiling point of 110 to 112 degrees centigrade at a pressure of 0.15 millimeter of mercury; n =l.5O31.

Analysis.-Calcd. for C I-1 0 C, 71.16; H, 8.53. Found: C, 69.93; H, 8.26.

Preparation 23.n-A myl Z-n-propoxybenzoate Using the procedure described in Preparation 1, but substituting n-amyl salicylate for n-butyl 4-hydroxybenzoate and l-bromopropane for allyl bromide, there was obtained n-amyl 2-n-propoxybenzoate in the form of an oil having a boiling point of 107 degrees centigrade at a pressure of 0.2 millimeter of mercury; n =1.4994.

AnaIysis.-Calcd. for C H O C, 71.97; H, 8.86. Found: C, 71.81; H, 9.22.

Preparation 24.-n-Amyl Z-n-amylOxybenzoate Using the procedure described in Preparation 1, but substituting n-amyl salicylate for n-butyl 4-hydroxybenzoate and n-amyl bromide for allyl bromide, there was obtained n-amyl 2-n-amyloxybenzoate in the form of an oil having a boiling point of 136 to 147 degrees centigrade at a pressure of 0.85 millimeter of mercury; n =1.4956.

'Analysz's.-Calcd. for C 7H O3: C, 73.34; H, 9.41 Found: C, 72.75; H, 9.05.

Preparation 25.--n-Amyl Z-n-hexyloxybenzoate Using the procedure described in.Preparation 1, but substituting n-amyl salicylate for n-butyl 4-hydroxybenzoate and n-hexyl bromide for allyl bromide, there was obtained n-amyl Z-n-hexyloxybenzoate in the form of an oil having a boiling point of 163 to 165 degrees centigrade at a pressure of 0.4 millimeter of mercury; n =1.4887.

Preparation 26.n-Amyl 2-n-heptyloxybenzoate Using the procedure described in Preparation 1, but substituting n-amyl salicylate for n-butyl 4-hydroxybenzoate and n-heptyl bromide for allyl bromide, there was obtained n-amyl Z-n-heptyloxybenzoate in the form of an oil having a boiling point of 158 to 160 degrees centigrade at a pressure of 0.3 millimeter of mercury; n =1.4929.

meter of mercury;

Found: C, 72.22; H, 8.67.

Found: C, 72.18; H, 8.82.

Preparation 28.n-Hexyl Z-eflzoxybenzoate Using the procedure described in Preparation 1, but substituting n-hexyl salicylate for n-butyl 4-hydroxybenzoate, ethyl iodide for allyl bromide and methyl ethyl ketone for acetone, there was obtained n-hexyl Z-ethoxybenzoate in the form of an oil having a boiling point of 110 to 112 degrees Centigrade at a pressure of 0.15 milli meter of mercury; n :1.5011.

Analysis.CalCd. for (3 1-1 C, 71.97; H, 8.86.

, Preparation 29.?-n-Hexyl Z-n-propaxybenzoate n Using the procedure described in Preparation 1, but substituting n-hexyl salicylate for n-butyl 4-hydroxybenzoate and l-brornopropane for allyl bromide, there was obtained n-hexyl Z-n-propoxybenzoate in the form of an oil having a boiling point of 118 to 130 degrees centigrade at a pressure'of 0.2 millimeter of mercury; n =1.4977.

Analysis.Calcd. for C H O C, 72.69; I-I, 9.15.

Found: C, 72.29; H, 9.10.

Preparation 3 0.-n-H exyl 2-n-but0xy benzoate Using the. procedure described in Preparation 12, but substituting n-hexyl salicylate for ethyl salicylate and'nbutyl bromide for l-bromopropane, there was obtained nhexyl Z-n-butoxybenzoate in the form of an oil having a boiling point of 115 to 116 degrees centigrade at a pressure of 0.05 millimeter of mercury; n =1.5014.

Analysis.-Calcd. for C H O C, 73.34; H, 9.41. Found: C, 73.45; H, 8.78.

Preparation 31.n-Butyl 3-allyl0xybenzoate n-Butyl B-hydroxybenzoate was prepared, using the procedure described in Preparation 2(a) but substituting 3- hydroxybenzoic acid for 4-hydroxybenzoic acid and nhutyl alcohol for n-amyl alcohol, in the form of an oil having a boiling point of 127 to 130 degrees centigrade at a pressure of 0.2'millimeter of mercury. Using the procedure described in Preparation 1, but substituting n-butyl 3-hydroxybenzoate for n-butyl 4-hydroxybenzoate, there was obtained n-butyl 3-allyloxybenzoate in the form of an oil having a boiling point of 120 degrees centigrade at a pressure of 0.4 millimeter of mercury; 7 :15090.

Analysis.-Calcd. for C I-1 0 C, 71.77; H, 7.74. FoundzuC, 71.66; H,8.14. I

Preparation 32.n-i3a tyl d-n-propoxybenzoate Using the procedure described in Preparation 1, but

' substituting n-butyl 3-hydroxybenzoate for n-butyl 4-hydroxybenzoate and l-bromopr-opane for 'allyl bromide, there was obtained n-butyl-3-n-propoxybenzoate in the form of an oil which had a boiling point'of 111-112 degrees centigrade at a presure of 0.2 millimeter of mercury;

Analysis.Calcd. for (3 11 0 Found: C, 71.03; H, 8.16.

Preparation 33.--n-Amyl 2-n-pr0poxybert20ate.

Using essentially the procedure described in Preparation 2(a) but substituting Z-n-propoxybenzdic acid for 4-hydroxybenzoic acid, there was obtained n-amyl Z-n-propoxybenzoate identical with the compound obtained in Preparation 23. v 1

grade at apressure of 0.1 millimeter =1.5l07.

l2 Preparation 34.-n-Butyl 2-(2-niethallyloxy)benzoate 4 Using the procedure described in Preparation 12, but substituting n-butyl salicylate for ethyl salicylate and 2- methallyl chloride for l-bromopropane, there was obtained n-butyl Z-(Z-methallyloxy)benzoate' in the form of an oil having a boiling point of 110 to 112 degrees centiof mercury; n

. Analysis.-Calcd. for (2, 11, 0 c, 72.55; H, 8.12. Found: c, 72.04; H, 7.88.

B. EXAMPLES ILLUSTRATING THE HERBICIDAL COMPOSITIONS OF THE INVENTION EXAMPLE 1 An emulsifiable concentrate, suitable for dilution with Water to give a herbicidal emulsion, was prepared by dissolving twelvegrams of Triton X-100 (an alkylaryl polyet-her alcohol) andfour grams of Agrimul 70A (a proprietary mixture of non-ionicsurfactants) in 84 grams of n butyl 2-allyloxybenzoate. taining 6000 parts per million of active ingredient, 27.2

To prepare an emulsion con grams of the emulsifiable concentrate so obtained is added to one gallon of water with vigorous stirring. To pre:

pare an emulsion containing 8000'parts per million of active ingredient, 36.2 grams of the above emulsifiable concentrate is added to one gallon of water with vigorous stirring. I

In place of the n-butyl Z-allyloxybenzoate employed as active ingredient in the above compositions, there can be employed any other compound having the Formula I as hereinbeiore described and exemplified.

' 7 EXAMPLE 2 An emulsifiable concentrate, suitable for dilution with water to give a herbicidal emulsion, was prepared 'by dissolving forty grams of n-butyl Z-n-propoxybenzoate and twenty grams of Triton X-100 in 140 grams of Carbitol (diethylene glycol monoethyl ether). To prepare an emulsion containing 6000 parts per million of active ingredient, 114 grams of the emulsifiable concentrate so obtained is added to one-gallon of Water with vigorous stirring. V

In place of the n-butyl 'Z-n-propoxybenzoate employed as active ingredient in the above compositions, there can be employed any other compound having the Formula I as hereinbefore described and exemplified.

EXAMPLE 3 v A dispersible powder suitable for addition to water to form an aqueous dispersion was prepared by mixing intimately three grams of n-amyl 2-allyloxybenzoate and twenty grams of Microcel 8 (a proprietary calcium silicate having a particle size of the order of five microns). To the product was added 0.5 gram of Pluronic F68 (an ethylene oxide-propylene glycol condensate) and the mixture .was 'macerated to give a fine-dry powder. This powder is added to one liter of water to give an aqueous dispersion containing 3000 parts per million of active ingredient. a

In place of. the n-amyl as active ingredient in the above composition there can be employed any other compound having the Formula I as hereinbefore described and exemplified.

It is to be understood that'the invention is not to be limited to the exact details of operation or compositions shown and described, as abvious modifications and equivalents will be apparent to one skilled in the art, and the invention is therefore to be limited only by the scope of the appended claims.

I claim: 7 w r 1. A method ofcontrolling undesired vegetation which comprises applying to the vegetation, in an amount suiti- 2-allyloxybenzoate employed cient to exert a herbicidal eifect, a compound having the formula:

wherein R and R represent lower aliphatic hydrocarbon radicals selected from the class consisting of alkyl having from 1 to 11 carbon atoms, inclusive, alkenyl having from 3 to 11 carbon atoms, inclusive, allrynyl having from 2 to 11 carbon atoms, inclusive, cycloalkyl having from 4 to 11 carbon atoms, inclusive, and cycloalkenyl having from 5 to 11 carbon atoms, inclusive, such that the total number of carbon atoms in the radicals R and R is not less than five and not more than twelve.

2. A method of controlling selectively the growth of crabgrass in the presence of growing desirable vegetation which comprises applying to the vegetation containing crabgrass, in an amount sutlicient to exert'herbicidal action, a compound having the formula:

wherein R and R represent lower aliphatic hydrocarbon radicals selected from the class consisting of alkyl having from 1 to 11 carbon atoms, inclusive, alkenyl having from 3 to 11 carbon atoms, inclusive, alkynyl having from 2 to 11 carbon atoms, inclusive, cycloalkyl having from 4m 11 carbon atoms, inclusive, and cycloalkenyl having from 5 to 11 carbon atoms, inclusive, such that the total number of carbon atoms in the radicals R and R is not less than five and not more than twelve.

3. A method of controlling selectively the growth of crabgrass in the presence of growingdesirable vegetation which comprises applying to the vegetation containing crabgrass, in an amount sufiicient to exert herbicidal action, a compound having the formula:

wherein R and R represent lower aliphatic hydrocarbon radicals selected from the class consisting of alkyl having eflective amount of n-butyl 2-allyloxybenzoate, a surfactant and a carrier. y

5. A herbicidal composition comprising a herbieidally effective amount of n-butyl 2-n-propoxybenzoate, a surfactant and a carrier.

6. A herbicidal composition comprising a herbicidally efiective amount of n-amyl 2-allyloxybenzoate, a surfactant and a carrier.

7. A herbicidal composition comprisng a herbicidally crabgrass in the presence of growing desirable vegetation which comprises applying to the vegetation containing cra'ograss, a herbicidal quantity of n-butyl 2-allyloxybenzoate.

9. A method of controlling selectively the growth of crabgrass in the presence of growing desirable vegetation which comprises applying to the vegetation containing crabgrass, a herbicidal quantity of n-amyl Z-allyloxybenzoate.

10. A method of controlling selectively the growth of crabg'rass in the presence of growing desirable vegetation which comprises applying to the vegetation containing crabgrass, a herbicidal quantity of n-butyl 2-n-proproxybenzoate.

11. A method of controlling selectively the growth of crabgrass in the presence of growing desirable vegetation which comprises applying to the vegetation containing crabgrass, a herbicidal quantity of ethyl Z-n-heptyloxybenzoate.

12. A method for controlling selectively the growth of undesired vegetation selected from the class consisting of crabgrass, white clover, oxalis, chickweed, foxtail, and Pan annua, in the presence of growing desirable vegetation, which comprises applying to the locus to be treated, in an amount sufiicient to kill said undesired Vegetation without significant damage to the desirable vegetation, a

compound having the formula:

to 11 carbon atoms, inclusive, and cycloalkenyl having from 5 to 11 carbon atoms, inclusive, such that the total number of carbon atoms in the radicals R and R is not less than five and not more than twelve.

References Cited by the Examiner UNITED STATES PATENTS 2,394,916 2/46 Jones 71--2.6 2,396,513' 3/46 Jones 71-2.6 2,577,969 12/51 Jones 712.6

OTHER REFERENCES King: Insecticides and Repellants, US. Dept. of

Agriculture, Agriculture Handbook, No. 69, pages 3-7 and 9-13.

Lespagnolet al. in Chemical Abstracts, vol. 33, col. 1295 (7), 1939.

Pierce et al. in Chemical Abstracts, vol. 3 7, col. 1409 King in Insecticides and Repellants, U.S. Department and 77.

of Agriculture, AgricultureHandbook No. 69, pages 76 JULIAN S. LEYITT, Primary Examiner.

G. D. MITCHELL, M. A. BRINDISI, LEWIS GOTTS, Examiners. 

1. A METHOD OF CONTROLLING UNDERSIRED VEGETATION WHICH COMPRISES APPLYING TO THE VEGETATION, IN AN AMOUNT SUFFICIENT TO EXERT A HERVICIDAL EFFECT, A COMPOUND HAVING THE FORMULA: 